Curable trans-1,2-cyclohexane bis(urea-urethane) compounds

ABSTRACT

Curable trans-1,2-cyclohexane bis(urea-urethane) compounds of the formulae 
                         
wherein R 1  and R′ 1  each, independently of the other, are alkylene, arylene, arylalkylene, or alkylarylene groups, R 2  and R′ 2  each, independently of the other, are alkyl, aryl, arylalkyl, or alkylaryl groups, R 3  and R′ 3  each, independently of the other, are hydrogen atoms or alkyl groups, R 4  and R′ 4  each, independently of the other, are hydrogen atoms, fluorine atoms, alkyl groups, or phenyl groups, n is an integer of 0, 1, 2, 3, or 4, and R 5  is an alkyl, aryl, arylalkyl, or alkylaryl group, or a substituent other than an alkyl, aryl, arylalkyl, or alkylaryl group, provided that at least one of R 1 , R′ 1 , R 2 , R′ 2 , R 3 , R′ 3 , R 4 , R′ 4 , or one or more of R 5  is an alkyl, alkylene, arylalkyl, arylalkylene, alkylaryl, or alkylarylene group containing an ethylenic unsaturation rendering the compound curable upon exposure to heat and/or actinic radiation.

CROSS-REFERENCE TO RELATED APPLICATIONS

Copending application U.S. Ser. No. 11/004,682, filed concurrentlyherewith, entitled “Trans-1,2-cyclohexane bis(urea-urethane) Compounds,”with the named inventors Adela Goredema, Rina Carlini, Marcel P. Breton,Jeffery H. Banning, and Eniko Toma, the disclosure of which is totallyincorporated herein by reference, discloses trans-1,2-cyclohexanebis(urea-urethane) compounds of the formulae

wherein R₁ and R′₁ each, independently of the other, is an alkylenegroup, an arylene group, an arylalkylene group, or an alkylarylenegroup, R₂ and R′₂ each, independently of the other, is an alkyl group,an aryl group, an arylalkyl group, or an alkylaryl group, R₃ and R′₃each, independently of the other, is a hydrogen atom or an alkyl group,R₄ and R′₄ each, independently of the other, is a hydrogen atom, afluorine atom, an alkyl group, or a phenyl group, n is an integer of 0,1, 2, 3, or 4, and R₅ is an alkyl group, an aryl group, an arylalkylgroup, an alkylaryl group, or a substituent other than an alkyl, aryl,arylalkyl, or alkylaryl group.

Copending application U.S. Ser. No. 11/004,332, filed concurrentlyherewith, entitled “Phase Change Inks Containing Trans-1,2-cyclohexanebis(urea-urethane) Compounds,” with the named inventors Adela Goredema,Rina Carlini, Marcel P. Breton, and Jeffery H. Banning, the disclosureof which is totally incorporated herein by reference, discloses phasechange inks comprising a phase change ink carrier and atrans-1,2-cyclohexane bis(urea-urethane) compound of the formula

or mixtures thereof, wherein R₁ and R′₁ each, independently of theother, is an alkylene group, an arylene group, an arylalkylene group, oran alkylarylene group, R₂ and R′₂ each, independently of the other, isan alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, R₃ and R′₃ each, independently of the other, is a hydrogen atomor an alkyl group, R₄ and R′₄ each, independently of the other, is ahydrogen atom, a fluorine atom, an alkyl group, or a phenyl group, n isan integer of 0, 1, 2, 3, or 4, and R₅ is an alkyl group, an aryl group,an arylalkyl group, an alkylaryl group, or a substituent other than analkyl, aryl, arylalkyl, or alkylaryl group.

Copending application U.S. Ser. No. 11/004,331, filed concurrentlyherewith, entitled “Bis(urea-urethane) Compounds and Phase Change InksContaining Same,” with the named inventors Adela Goredema, Rina Carlini,Christine E. Bedford, Marcel P. Breton, and Eniko Toma, the disclosureof which is totally incorporated herein by reference, discloses abis(urea-urethane) compound of the formula

wherein R₁ and R₁′ each, independently of the other, is an alkyl group,wherein at least one of R₁ and R₁′ has at least about 6 carbon atoms, R₂and R₂′ each, independently of the other, is an alkylene group, whereinat least one of R₂ and R₂′ has at least about 3 carbon atoms, R₃ is analkylene group having at least about 2 carbon atoms, and R₄ and R₅ each,independently of the other, is a hydrogen atom or an alkyl group, andwherein R₁ and R₁′ each contain no more than 2 fully fluorinated carbonatoms.

Copending application U.S. Ser. No. 11/004,333, filed concurrentlyherewith, entitled “Phase Change Inks Containing Bis(urea-urethane)Compounds,” with the named inventors Adela Goredema, Rina Carlini,Christine E. Bedford, and Marcel P. Breton, the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomposition comprising a phase change ink carrier and abis(urea-urethane) compound of the formula

wherein R₁ and R₁′ each, independently of the other, is an alkyl group,an aryl group, an arylalkyl group, or an alkylaryl group, R₂ and R₂′each, independently of the other, is an alkylene group, an arylenegroup, an arylalkylene group, or an alkylarylene group, R₃ is analkylene group, an arylene group, an arylalkylene group, or analkylarylene group, and R₄ and R₅ each, independently of the other, is ahydrogen atom or an alkyl group.

Copending application U.S. Ser. No. 60/633,331, filed concurrentlyherewith, entitled “Processes for Preparing Bis(urea-urethane)Compounds,” with the named inventor Adela Goredema, the disclosure ofwhich is totally incorporated herein by reference, discloses a processfor preparing bis(urea-urethane) compounds of the formula

wherein R₁ is an alkyl group, an aryl group, an arylalkyl group, or analkylaryl group, R₂ is an alkylene group, an arylene group, anarylalkylene group, or an alkylarylene group, R₃ is an alkylene group,an arylene group, an arylalkylene group, or an alkylarylene group, andR₄ is a hydrogen atom or an alkyl group, said process comprising: (1)first adding a monoalcohol reactant of the formula R₁—OH to adiisocyanate reactant of the formula OCN—R₂—NCO, said monoalcohol beingadded in an amount of from about 0.8 mole of monoalcohol per every onemole of diisocyanate to about 1.2 moles of monoalcohol per every onemole of diisocyanate, said monoalcohol and said diisocyanate reactantsbeing admixed in a solvent, said reactants and said solvent beingpresent in a relative amount of at least about 10 milliliters of solventper every 1 millimole of diisocyanate, said addition of monoalcoholoccuring while heating the diisocyanate and the solvent to a temperatureof from about 25° C. to about 125° C.; (2) subsequent to addition of themonoalcohol, maintaining the temperature of the reaction mixture thusformed at a temperature of from about 25° C. to about 125° C. until thereaction between the monoalcohol and the diisocyanate is complete; and(3) subsequent to step (2), adding to the reaction mixture a diamine ofthe formula

without isolating the reaction product of step (2), thereby forming acompound of the formula

in desirably high yield.

Copending application U.S. Ser. No. 11/004,451, filed concurrentlyherewith, entitled “Phase Change Inks Containing CurableTrans-1,2-cyclohexane bis(urea-urethane) Compounds,” with the namedinventors Rina Carlini, Eniko Toma, Peter G. Odell, and Jeffery H.Banning, the disclosure of which is totally incorporated herein byreference, discloses phase change inks comprising a phase change inkcarrier and one or more curable trans-1,2-cyclohexane bis(urea-urethane)compounds of the formulae

wherein R₁ and R′₁ are alkylene, arylene, arylalkylene, or alkylarylenegroups, R₂ and R′₂ are alkyl, aryl, arylalkyl, or alkylaryl groups, R₃and R′₃ are hydrogen atoms or alkyl groups, R₄ and R′₄ are hydrogenatoms, fluorine atoms, alkyl groups, or phenyl groups, n is an integerof 0, 1, 2, 3, or 4, and R₅ is an alkyl, aryl, arylalkyl, or alkylarylgroup, or a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, provided that at least one of R₁, R′₁, R₂, R′₂, R₃,R′₃, R₄, R′₄, or one or more of R₅ is an alkyl, alkylene, arylalkyl,arylalkylene, alkylaryl, or alkylarylene group containing an ethyleneunsaturation rendering the compound curable upon exposure to heat and/oractinic radiation.

Copending application U.S. Ser. No. 09/949,315, filed Sep. 7, 2001, U.S.Publication 20030079644, entitled “Aqueous Ink Compositions,” with thenamed inventors Thomas W. Smith, David J. Luca, and Kathleen M. McGrane,the disclosure of which is totally incorporated herein by reference,discloses an aqueous ink composition comprising an aqueous liquidvehicle, a colorant, and an additive wherein, when the ink has beenapplied to a recording substrate in an image pattern and a substantialamount of the aqueous liquid vehicle has either evaporated from the inkimage, hydrogen bonds of sufficient strength exist between the additivemolecules so that the additive forms hydrogen-bonded oligomers orpolymers.

Copending application U.S. Ser. No. 09/948,958, filed Sep. 7, 2001, U.S.Publication 20030105185, entitled “Phase Change Ink Compositions,” withthe named inventors H. Bruce Goodbrand, Thomas W. Smith, Dina Popovic,Daniel A. Foucher, and Kathleen M. McGrane, the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomposition comprising a colorant and an ink vehicle, the ink being asolid at temperatures less than about 50° C. and exhibiting a viscosityof no more than about 20 centipoise at a jetting temperature of no morethan about 160° C., wherein at a first temperature hydrogen bonds ofsufficient strength exist between the ink vehicle molecules so that theink vehicle forms hydrogen-bonded dimers, oligomers, or polymers, andwherein at a second temperature which is higher than the firsttemperature the hydrogen bonds between the ink vehicle molecules aresufficiently broken that fewer hydrogen-bonded dimers, oligomers, orpolymers are present in the ink at the second temperature than arepresent in the ink at the first temperature, so that the viscosity ofthe ink at the second temperature is lower than the viscosity of the inkat the first temperature.

Copending application U.S. Ser. No. 10/770,305, filed Feb. 2, 2004, U.S.Publication 20040158063, entitled “Alkylated Tetrakis(triaminotriazine)Compounds and Phase Change Inks Containing Same,” with the namedinventors Danielle C. Boils Boissier, Marcel P. Breton, Jule W. Thomas,Jr., Donald R. Titterington, Jeffery H. Banning, H. Bruce Goodbrand,James D. Wuest, Marie È{grave over (v)}è Perron, Francis Monchamp, andHugues Duval, the disclosure of which is totally incorporated herein byreference, discloses compounds of the formulae

wherein, provided that at least one of R₁, R₂, R₃, R₄, R₅, and R₆ is ahydrogen atom, and provided that at least one of R₁, R₂, R₃, R₄, R₅, andR₆ is not a hydrogen atom, R₁, R₂, R₃, R₄, R₅, and R₆ each,independently of the others, is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup. Also disclosed are phase change ink compositions comprising acolorant and a phase change ink carrier comprising a material of thisformula.

Copending application U.S. Ser. No. 10/235,061, filed Sep. 4, 2002, U.S.Publication 20040060474, and Copending application U.S. Ser. No.10/794,930, filed Mar. 5, 2004, both entitled “GuanidinopyrimidinoneCompounds and Phase Change Inks Containing Same,” with the namedinventors Danielle C. Boils-Boissier, Marcel P. Breton, Jule W. Thomas,Jr., Donald R. Titterington, Jeffery H. Banning, H. Bruce Goodbrand,James D. Wuest, Marie-È vePerron, and Hugues Duval, the disclosure ofwhich is totally incorporated herein by reference, discloses compoundsof the formulae

wherein, provided that at least one of R₁, R₂, and R₃ is not a hydrogenatom, R₁, R₂, and R₃ each, independently of the other, is (i) a hydrogenatom, (ii) an alkyl group, (iii) an aryl group, (iv) an arylalkyl group,or (v) an alkylaryl group, and wherein R₁ and R₂ can also be (vi) analkoxy group, (vii) an aryloxy group, (viii) an arylalkyloxy group, (ix)an alkylaryloxy group, (x) a polyalkyleneoxy group, (xi) apolyaryleneoxy group, (xii) a polyarylalkyleneoxy group, (xiii) apolyalkylaryleneoxy group, (xiv) a silyl group, (xv) a siloxane group,(xvi) a polysilylene group, (xvii) a polysiloxane group, or (xviii) agroup of the formula

wherein r is an integer representing a number of repeat —CH₂— groups,wherein s is an integer representing a number of repeating —CH₂— groups,and wherein X is (a) a direct bond, (b) an oxygen atom, (c) a sulfuratom, (d) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (e) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and R₁₀ and R₁₁ each,independently of the other, is (i) an alkylene group, (ii) an arylenegroup, (iii) an arylalkylene group, or (iv) an alkylarylene group, andwherein R₁₀ can also be (v) a polyalkyleneoxy group, (vi) apolyaryleneoxy group, (vii) a polyarylalkyleneoxy group, (viii) apolyalkylaryleneoxy group, (ix) a silylene group, (x) a siloxane group,(xi) a polysilylene group, or (xii) a polysiloxane group. Also disclosedare phase change ink compositions comprising a colorant and a phasechange ink carrier comprising a material of this formula.

Copending application U.S. Ser. No. 10/235,109, filed Sep. 4, 2002, U.S.Publication 20040075723, and Copending application U.S. Ser. No.10/810,370, filed Mar. 26, 2004, both entitled “Alkylated Urea andTriaminotriazine Compounds and Phase Change Inks Containing Same,” withthe named inventors Marcel P. Breton, Danielle C. Boils-Boissier, JuleW. Thomas, Jr., Donald R. Tifterington, H. Bruce Goodbrand, Jeffery H.Banning, James D. Wuest, Dominic Lalibertè, and Marie-È ve Perron, thedisclosure of which is totally incorporated herein by reference,discloses compounds of the formulae

wherein Z is a group of the formula —OR₁, a group of the formula —SR₁,or a group of the formula —NR₁R₂, Y is a group of the formula —OR₃, agroup of the formula —SR₃, or a group of the formula —NR₃R₄, n is aninteger representing the number of repeat —(CH₂)— or —(CH₂CH₂O)— units,wherein, provided that at least one of R₁, R₂, R₃, R₄, R₅, and R₆ is ahydrogen atom, provided that at least one of R₁, R₂, R₃, R₄, R₅, and R₆is other than a hydrogen atom, and provided that at least one Z or Ywithin the compound is a group of the formula —NR₁R₂ or a group of theformula —NR₃R₄, R₁, R₂, R₃, R₄, R₅, R₆, and R₇ each, independently ofthe others, is (i) a hydrogen atom, (ii) an alkyl group, (iii) an arylgroup, (iv) an arylalkyl group, or (v) an alkylaryl group, and whereinR₇ can also be (vi) an alkoxy group, (vii) an aryloxy group, (viii) anarylalkyloxy group, (ix) an alkylaryloxy group, (x) a polyalkyleneoxygroup, (xi) a polyaryleneoxy group, (xii) a polyarylalkyleneoxy group,(xiii) a polyalkylaryleneoxy group, (xiv) a silyl group, (xv) a siloxanegroup, (xvi) a polysilylene group, (xvii) a polysiloxane group, or(xviii) a group of the formula

wherein r is an integer representing a number of repeat —CH₂— groups,wherein s is an integer representing a number of repeating —CH₂— groups,and wherein X is (a) a direct bond, (b) an oxygen atom, (c) a sulfuratom, (d) a group of the formula —NR₄₀— wherein R₄₀ is a hydrogen atom,an alkyl group, an aryl group, an arylalkyl group, or an alkylarylgroup, or (e) a group of the formula —CR₅₀R₆₀— wherein R₅₀ and R₆₀ each,independently of the other, is a hydrogen atom, an alkyl group, an arylgroup, an arylalkyl group, or an alkylaryl group, and wherein R₆ canalso be

Also disclosed are phase change ink compositions comprising a colorantand a phase change ink carrier comprising a material of this formula.

Copending application U.S. Ser. No. 10/235,125, filed Sep. 4, 2002, U.S.Publication 20040065227, entitled “Phase Change Inks Containing GelatorAdditives,” with the named inventors Marcel P. Breton, Danielle C.Boils-Boissier, Donald R. Titterington, Jule W. Thomas, Jr., Jeffery H.Banning, Christy Bedford, and James D. Wuest, the disclosure of which istotally incorporated herein by reference, discloses a phase change inkcomposition comprising an ink vehicle, a colorant, and a nonpolymericorganic gelator selected from the group consisting of anthracene-basedcompounds, steroid compounds, partially fluorinated high molecularweight alkanes, high molecular weight alkanes with exactly one heteroatom, chiral tartrate compounds, chiral butenolide-based compounds,bis-urea compounds, guanines, barbiturates, oxamide compounds,ureidopyrimidone compounds, and mixtures thereof, said organic gelatorbeing present in the ink in an amount of no more than about 20 percentby weight of the ink, said ink having a melting point at or below whichthe ink is a solid, said ink having a gel point at or above which theink is a liquid, and said ink exhibiting a gel state between the meltingpoint and the gel point, said ink exhibiting reversible transitionsbetween the solid state and the gel state upon heating and cooling, saidink exhibiting reversible transitions between the gel state and theliquid state upon heating and cooling, said melting point being greaterthan about 35° C., said gel point being greater than said melting point.Also disclosed are imaging processes employing phase change inkscontaining gelator additives.

BACKGROUND

Disclosed herein are curable trans-1,2-cyclohexane bis(urea-urethane)compounds. More specifically, disclosed herein are some curabletrans-1,2-cyclohexane bis(urea-urethane) compounds and hot melt or phasechange inks containing these compounds. One embodiment is directed tocurable trans-1,2-cyclohexane bis(urea-urethane) compounds of theformulae

wherein R₁ and R′₁ each, independently of the other, is an alkylenegroup, an arylene group, an arylalkylene group, or an alkylarylenegroup, R₂ and R′₂ each, independently of the other, is an alkyl group,an aryl group, an arylalkyl group, or an alkylaryl group, R₃ and R′₃each, independently of the other, is a hydrogen atom or an alkyl group,R₄ and R′₄ each, independently of the other, is a hydrogen atom, afluorine atom, an alkyl group, or a phenyl group, n is an integer of 0,1, 2, 3, or 4, and R₅ is an alkyl group, an aryl group, an arylalkylgroup, an alkylaryl group, or a substituent other than an alkyl, aryl,arylalkyl, or alkylaryl group, provided that at least one of R₁, R′₁,R₂, R′₂, R₃, R′₃, R₄, R′₄, or one or more of R₅ is an alkyl, alkylene,arylalkyl, arylalkylene, alkylaryl, or alkylarylene group containing anethylenic unsaturation rendering the compound curable upon exposure toheat and/or actinic radiation.

In general, phase change inks (sometimes referred to as “hot melt inks”)are in the solid phase at ambient temperature, but exist in the liquidphase at the elevated operating temperature of an ink jet printingdevice. At the jet operating temperature, droplets of liquid ink areejected from the printing device and, when the ink droplets contact thesurface of the recording substrate, either directly or via anintermediate heated transfer belt or drum, they quickly solidify to forma predetermined pattern of solidified ink drops. Phase change inks havealso been used in other printing technologies, such as gravure printing,as disclosed in, for example, U.S. Pat. No. 5,496,879 and German PatentPublications DE 4205636AL and DE 4205713AL, the disclosures of each ofwhich are totally incorporated herein by reference.

Phase change inks for color printing typically comprise a phase changeink carrier composition which is combined with a phase change inkcompatible colorant. In a specific embodiment, a series of colored phasechange inks can be formed by combining ink carrier compositions withcompatible subtractive primary colorants. The subtractive primarycolored phase change inks can comprise four component dyes, namely,cyan, magenta, yellow and black, although the inks are not limited tothese four colors. These subtractive primary colored inks can be formedby using a single dye or a mixture of dyes. For example, magenta can beobtained by using a mixture of Solvent Red Dyes or a composite black canbe obtained by mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat.No. 4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each ofwhich are totally incorporated herein by reference, teach that thesubtractive primary colorants employed can comprise dyes from theclasses of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified Acidand Direct Dyes, and Basic Dyes. The colorants can also includepigments, as disclosed in, for example, U.S. Pat. No. 5,221,335, thedisclosure of which is totally incorporated herein by reference. U.S.Pat. No. 5,621,022, the disclosure of which is totally incorporatedherein by reference, discloses the use of a specific class of polymericdyes in phase change ink compositions.

Phase change inks have also been used for applications such as postalmarking, industrial marking, and labelling.

Phase change inks are desirable for ink jet printers because they remainin a solid phase at room temperature during shipping, long term storage,and the like. In addition, the problems associated with nozzle cloggingas a result of ink evaporation with liquid ink jet inks are largelyeliminated, thereby improving the reliability of the ink jet printing.Further, in phase change ink jet printers wherein the ink droplets areapplied directly onto the final recording substrate (for example, paper,transparency material, and the like), the droplets solidify immediatelyupon contact with the substrate, so that migration of ink along theprinting medium is prevented and dot quality is improved.

Compositions suitable for use as phase change ink carrier compositionsare known. Some representative examples of references disclosing suchmaterials include U.S. Pat. No. 3,653,932, U.S. Pat. No. 4,390,369, U.S.Pat. No. 4,484,948, U.S. Pat. No. 4,684,956, U.S. Pat. No. 4,851,045,U.S. Pat. No. 4,889,560, U.S. Pat. No. 5,006,170, U.S. Pat. No.5,151,120, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,496,879, EuropeanPatent Publication 0187352, European Patent Publication 0206286, GermanPatent Publication DE 4205636AL, German Patent Publication DE 4205713AL,and PCT Patent Application WO 94/04619, the disclosures of each of whichare totally incorporated herein by reference. Suitable carrier materialscan include paraffins, microcrystalline waxes, polyethylene waxes, esterwaxes, fatty acids and other waxy materials, fatty amide containingmaterials, sulfonamide materials, resinous materials made from differentnatural sources (tall oil rosins and rosin esters, for example), andmany synthetic resins, oligomers, polymers, and copolymers.

U.S. Pat. No. 6,761,758 (Boils-Boissier et al.), the disclosure of whichis totally incorporated herein by reference, discloses compounds of theformulae

wherein, provided that at least one of R₁, R₂, R₃, R₄, R₅, and R₆ is ahydrogen, atom, and provided that at least one of R₁, R₂, R₃, R₄, R₅,and R₆ is not a hydrogen atom, R₁, R₂, R₃, R₄, R₅, and R₆ each,independently of the others, is (i) a hydrogen atom, (ii) an alkylgroup, (iii) an aryl group, (iv) an arylalkyl group, or (v) an alkylarylgroup. Also disclosed are phase change ink compositions comprising acolorant and a phase change ink carrier comprising a material of thisformula.

U.S. Pat. No. 6,471,758 and European Patent Publication EP 1 067 157(Kelderman et al.), the disclosures of each of which are totallyincorporated herein by reference, disclose an ink composition for ameltable ink usable in a printing device in which ink drops are ejectedfrom ink ducts, which comprises agents which reversibly cross-link theink, the said agents containing a gelling agent. When an ink drop whichhas been transferred to a substrate passes over into a gel during thecooling process, the consequence is that the viscosity of the melted inkdrop increases greatly so that the drops become relatively immobile. Inthis way the ink drops are prevented from uncontrollably flowing intothe paper. As a result, inks of this kind are suitable for use on bothporous and smooth substrates. In addition, these inks have been foundsuitable for use in a printing device in which printed substrates aresubjected to thermal after-treatment.

“Cyclic Bis-Urea Compounds as Gelators for Organic Solvents,” J. vanEsch et al., Chem. Eur. J. 1999, 5, No. 3, pp. 937-950, the disclosureof which is totally incorporated herein by reference, discloses thestudy of the gelation properties of bis-urea compounds derived fromoptically pure trans-1,2-diaminocyclohexane and 1,2-diaminobenzene, withpendant aliphatic, aromatic, or ester groups, as well as the structureof the resulting gels.

“The Design of Organic Gelators Based on a Family of Bis-Ureas,” R. E.Melèndez et al., Mat. Res. Soc. Symp. Proc. 2000, 604, pp. 335-340, thedisclosure of which is totally incorporated herein by reference,discloses a study of the organogelation properties of a family ofbis-ureas.

“Formation of Organogels by Intermolecular Hydrogen Bonding BetweenUreylene Segment,” K. Hanabusa et al., Chem. Lett. 1996 pp. 885-886, thedisclosure of which is totally incorporated herein by reference,discloses low molecular weight compounds having ureylene segment causingphysical gelation in organic solvents. The main driving force forgelation was intermolecular hydrogen bonding between ureylene units.

“Low Molecular Weight Gelators for Organic Solvents,” J. van Esch etal., in Supromolecular Science: Where Is It and Where It Is Going, R.Ungaro and E. Dalcanale, Eds., 1999, Netherlands: Kluwer AcademicPublishers, pp. 233-259, the disclosure of which is totally incorporatedherein by reference, discloses the gelation of solvents byorganogelators.

“Organogels and Low Molecular Mass Organic Gelators,” D. J. Abdallah andR. G. Weiss, Adv. Mater. 2000, 12, No. 17, September 1, pp. 1237-1247,the disclosure of which is totally incorporated herein by reference,discloses the stepwise simplification of low molecular-mass organicgelator structures and the development of methods to determine theirpacking in organogels at the micrometer-to-angstrom distance regimes, aswell as an overview of current and potential applications for thesematerials.

“Remarkable Stabilization of Self-Assembled Organogels byPolymerization,” M. de Loos et al., J. Am. Chem. Soc. 1997, 119,12675-12676, the disclosure of which is totally incorporated herein byreference, discloses studies of polymerizable bis(amido)cyclohexane andbis(ureido)cyclohexane derivatives, investigating their gelatingcapacity for organic solvents.

“Low-molecular weight organogelators,” P. Terech, in SpecialistSurfactants, I. D. Robb, Ed., 1997, London: Chapman & Hall, pp. 208-68,the disclosure of which is totally incorporated herein by reference,discloses a special class of surfactants which have the ability to formviscoelastic fluids or solid-like materials in organic solvents atconcentrations lower than about 2 percent.

“New Functional Materials Based on Self-Assembling Organogels: FromSerendipity Towards Design,” J. H. van Esch and B. L. Feringa, Angew.Chem. Int. Ed. 2000, 39, No. 13, pp. 2263-2266, the disclosure of whichis totally incorporated herein by reference, discloses a review ofdevelopments in the field of organogels.

“Synthesis and Self-Assembling Properties of PolymerizableOrganogelators,” G. Wang and A. D. Hamilton, Chem. Eur. J. 2002, 8, No.8, pp. 1954-1961, the disclosure of which is totally incorporated hereinby reference, discloses the development of a family of polymerizableurea derivatives that are gelators for organic solvents.

“Low Molecular Mass Gelators of Organic Liquids and the Properties oftheir Gels,” P. Terech and R. G. Weiss, Chem. Rev. 1997, 97, pp.3133-3159, the disclosure of which is totally incorporated herein byreference, discloses a review of the properties of thermally-reversibleviscoelastic liquidlike or solidlike organogels comprising an organicliquid and low concentrations of relatively low molecular mass gelatormolecules.

“Towards a Phenomenological Definition of the Term ‘Gel’,” K. Amdal etal., Polymer Gels and Networks, 1993, 1, pp. 5-17, the disclosure ofwhich is totally incorporated herein by reference, discusses existingdefinitions of the term “gel” and proposes specific uses of the term.

PCT Patent Publication WO 03/084508 and European Patent Publication EP 1350 507 (Friesen et al.), the disclosures of each of which are totallyincorporated herein by reference, disclose delivery vehicles fordelivering a substance of interest to a predetermined site, said vehiclecomprising said substance and a means for inducing availability of atleast one compartment of said vehicle toward the exterior, therebyallowing access of said substance to the exterior of said vehicle atsaid predetermined site. The invention is further concerned with uses ofsaid vehicle and methods for preparing it.

PTC Patent Publication WO 03/040135 (Dowle et al.), the disclosure ofwhich is totally incorporated herein by reference, discloses compoundsof the formula

in which R is an amino or guanidino group, R₂ is acetyl ortrifluoroacetyl, X is CONH, SO₂NH, NHCO, or NHCONH, m is either 0 or 1,n is an integer from 2 to 6, q is an integer from 0 to 3, and Y ishydrogen or an aromatic substituent, or a pharmaceutically acceptablederivative thereof. Also disclosed are methods for their preparation,pharmaceutical formulations containing them, and their use in theprevention or treatment of a viral infection.

PTC Patent Publication WO 00/55149 and U.S. Pat. No. 6,548,476 (Wu etal.), the disclosures of each of which are totally incorporated hereinby reference, disclose dimeric compounds, methods for their preparation,pharmaceutical formulations thereof, and their use as antiviral agents.The compounds are particularly useful against influenza virus. Inparticular the references disclose a dimeric compound which comprisestwo neuraminidase binding groups attached to a spacer or linking group.Preferably the dimeric molecule comprises two neuraminidase-bindingneuraminic acid (sialic acid) or cyclopentyl or cyclohexenyl carboxylicacid derivatives covalently attached to a common spacer group.Pharmaceutical compositions and methods of treatment, prophylaxis anddiagnosis are disclosed and claimed.

U.S. Patent Publication 20010044553 (Kabashima et al.), the disclosureof which is totally incorporated herein by reference, discloses aurea-urethane compound having one or more urea groups and one or moreurethane groups in the molecular structure, the number of said ureagroups (A) and the number of said urethane groups (B) satisfying thefollowing numerical formula: 10≧(A+B)≧3 wherein each of A and B is aninteger of 1 or more.

European Patent Publication EP 1 048 681 and U.S. Pat. No. 6,420,466(Haubennestel et al.), the disclosures of each of which are totallyincorporated herein by reference, disclose a process for preparing asolution that is active as a thixotropic agent and contains ureaurethanes, in which monohydroxyl compounds are reacted with an excess oftoluene diisocyanate, the unreacted portion of the toluene diisocyanateis removed from the reaction mixture, and the monosiocyanate adductobtained is further reacted with diarines in the presence of a lithiumsalt to form urea urethanes. The invention also relates to the use ofthe solution for imparting thixotropic properties to coating compounds.

Japanese Patent Publication JP 10310633, the disclosure of which istotally incorporated herein by reference, discloses a cationic curingcatalyst composition improved in stability during storage at roomtemperature or above and suppressed in increase in viscosity, using atleast one stabilizer selected from the compounds containing a urethanebond, an amide bond, a urea bond and a carbodiimide group in themolecule and a dialkylaminopyridine compound or a proton acid compound.

European Patent Publication EP 0 056 153 and U.S. Pat. No. 4,384,102(Rasshofer et al.), the disclosures of each of which are totallyincorporated herein by reference, disclose compounds having boths-triazine units and epoxide groups present that are prepared byreacting an epoxide containing an isocyanate-reactive group with atriisocyanate corresponding to the formula

in which X is as defined therein. These reactants are used in quantitiessuch that the equivalent ratio of isocyanate groups toisocyanate-reactive groups is maintained at less than or equal to 1to 1. The compounds thus produced are particularly useful as reactivecross-linkers in the production of polyurethanes and polyepoxides.

European Patent Publication EP 0 160 402 and U.S. Pat. No. 4,566,981(Howells), the disclosures of each of which are totally incorporatedherein by reference, disclose cationic and non-ionic fluorochemicals,mixtures of cationic and non-ionic fluorochemicals, blends of themixtures with fluorochemical poly(oxyalkylenes), and compositions of thefluorochemicals with hydrocarbon nonionic surfactants. Thesefluorochemicals and compositions, in dispersions, emulsions andmicroemulsions, may be applied to porous fibrous substrates to give oiland water repellency and soil resistance.

Japanese Patent Publication JP 59030919, the disclosure of which istotally incorporated herein by reference, discloses a method to preventthe bad influence of a treatment on spinning properties and drawingproperties of synthetic yarn, by providing undrawn yarn of melt spinningwith a spinning oil, applying a specific treatment to it, drawing andheat-treating it. The undrawn yarn which is prepared by melt spinningand cooled is provided with a spinning oil by the oil applicator, coatedwith a treatment by the treatment applicator, sent through the taking uproller and the drawing rollers, and wound around the winder. Thetreatment is a compound shown by the formula(R_(f)-A-B₁—CONH—X—NHCO—B₂—)_(n)Y (R_(f) is 4-16C perfluoroalkyl; A is—(CH₂)_(x1)—, CON(R₁)—(CH₂)_(x2)—, or SO₂N(R₁)—(CH₂)_(x2)—; x1 is 1-20integer; x2 is 1-12 integer; R₁ is H, or 1-6C alkyl; B₁ and B₂ are —O—,—S—, or —N(R₂)—; R₂ is H, or 1-4C alkyl; X is bifunctional organicgroup; Y is polyfunctional organic group; n is 2-10 integer) and itspickup is 0.03-2.0 wt %.

Compounds that enable gelation are also disclosed in, for example:“Reversible Polymers Formed from Self-Complementary Monomers UsingQuadruple Hydrogen Bonding,” R. P. Sijbesma et al., Science, Vol. 278,p. 1601 (1997); “Supramolecular Polymers,” R. Dagani, Chemical andEngineering News, p. 4 (December 1997); “Supramolecular Polymers fromLinear Telechelic Siloxanes with Quadruple-Hydrogen-Bonded Units,” J. H.K. Hirschberg et al., Macromolecules, Vol. 32, p. 2696 (1999); “Designand Synthesis of ‘Smart’ Supramolecular Liquid Crystalline Polymers viaHydrogen-Bond Associations,” A. C. Griffin et al., PMSE Proceedings,Vol. 72, p. 172 (1995); “The Design of Organic Gelators: Solution andSolid State Properties of a Family of Bis-Ureas,” Andrew J. Carr et al.,Tetrahedron Letters, Vol. 39, p. 7447 (1998); “Hydrogen-BondedSupramolecular Polymer Networks,” Ronald F. M. Lange et al., Journal ofPolymer Science, Part A: Polymer Chemistry, Vol. 37, p. 3657 (1999);“Combining Self-Assembly and Self-Association—Towards ColumnarSupramolecular Structures in Solution and in Liquid-CrystallineMesophase,” Arno Kraft et al., Polym. Mater. Sci. Eng., Vol. 80, p. 18(1999); “Facile Synthesis of β-Keto Esters from Methyl Acetoacetate andAcid Chloride: The Barium Oxide/Methanol System,” Y. Yuasa et al.,Organic Process Research and Development, Vol. 2, p. 412 (1998);“Self-Complementary Hydrogen Bonding of1,1′-Bicyclohexylidene-4,4′-dione Dioxime. Formation of a Non-CovalentPolymer,” F. Hoogesteger et al., Tetrahedron, Vol. 52, No. 5, p. 1773(1996); “Molecular Tectonics. Three-Dimensional Organic Networks withZeolite Properties,” X. Wang et al., J. Am. Chem. Soc., Vol. 116, p.12119 (1994); “Helical Self-Assembled Polymers from Cooperative Stackingof Hydrogen-Bonded Pairs,” J. H. K. Ky Hirschberg et al., Nature, Vol.407, p. 167 (2000); “New Supramolecular Arrays based on Interactionsbetween Carboxylate and Urea Groups: Solid-State and Solution Behavior,”Abdullah Zafar et al., New J. Chem., 1998, 137-141; U.S. Pat. No.6,320,018; U.S. Pat. No. 5,892,116; PCT Patent Publication WO 97/24364;“The Unusual Molecular Organization of 2,3-Bis(n-hexyloxy)-anthracene inthe Crystal. A Hint to the Origin of the Gelifying Properties of2,3-Bis(n-alkyloxy)anthracenes?”, J-L. Pozzo et al., J. Chem. Soc.,Perkin Trans., 2, 824-826 (2001); “The Quest for the Simplest PossibleOrganogelators and Some Properties of their Organogels,” D. Abdallah etal., J. Braz. Chem. Soc., Vol. 11, No. 3, 209-218 (2000); “OrganogelElectrolytes Based on a Low Molecular Weight Gelator:2,3-Bis(n-decyloxy)anthracene,” F. Placin et al., Chem. Mater. 13,117-121 (2001); “Novel Vesicular Aggregates of Crown-AppendedCholesterol Derivatives Which Act as Gelators of Organic Solvents and asTemplates for Silica Transcription,” J. Jung et al., J. Am. Chem. Soc.,Vol. 122, No. 36, 8648-8653 (2000); “n-Alkanes Gel n-Alkanes (and ManyOther Organic Liquids),” D. Abdallah et al., Langmuir, 16, 352-355(2000); “Low Molecular Mass Gelators of Organic Liquids and theProperties of their Gels,” P. Terech et al., Chem. Rev., 97, 3133-3159(1997); “Organogels and Low Molecular Mass Organic Gelators,” D.Abdallah et al., Adv. Mater., 12, No. 17, 1237 (2000); “Making it AllStick Together: the Gelation of Organic Liquids by Small OrganicMolecules,” F. Schoonbeek, Doctoral Thesis, U. of Groningen,Netherlands, April 2001; Twieg et al., Macromolecules, Vol. 18, p. 1361(1985); “Synthesis and Reactions of Polyhydric Alcohols I. Synthesis andReactions of p-Toluenesulfonates of Polyhydric Alcohols,” ZhurnalObshchei Khimii, Vol. 35, No. 5, p. 804-807 (1965); “The Chemotherapy ofSchistosomiasis. Part I. Derivatives and Analogs ofαω-Di-(p-aminophenoxy)alkanes,” J. Ashley et al., J. Chem. Soc. 1958,3293; “Remarkably Simple Small Organogelators: Di-n-alkoxy-benzeneDerivatives,” G. Clavier et al., Tetrahedron Letters, 40, 9021-9024(1999); “Rational Design of Low Molecular Mass Organogelators: Toward aLibrary of Functional N-Acyl-1-ω-Amino Acid Derivatives,” G.Mieden-Gundert et al., Angew. Chem. Int. Ed., 40, No. 17, 3164-3166(2001); U.S. Pat. No. 2,703,808; “Rational Design of New Acid-SensitiveOrganogelators,” J-L. Pozzo et al., J. Mater. Chem., Vol. 8, pp.2575-2577 (1998); J. T. Thurston et al., J. Am. Chem. Soc., Vol. 73, pp.2981-3008 (1951); J. Am. Chem. Soc., Vol. 96, pp. 1082-1087 (1974); J-L.Pozzo et al., Tetrahedron, Vol. 53, No. 18, pp. 6377-6390 (1997); J-L.Pozzo et al., Mol. Cryst. Liq. Cryst., Vol. 344, pp. 101-106 (2000); Y.C. Lin, R. G. Weiss, Macromolecules, Vol. 20, p. 414 (1987); U.S. Pat.No. 4,790,961; Murata et al, J. Am. Chem. Soc., Vol. 116, No 15, pp.6664-6676 (1994); A. Ikeda et al., Rep. Asahi Glass Found. Ind.Technol., Vol. 61, p. 115, (1992); Rabolt et al., Macromolecules, Vol.17, p. 2786 (1984); D. J. Abdallah et al., Chem. Mater., Vol. 11, p.2907 (1999); Ralston et al., J. Org. Chem., Vol. 9, p. 259 (1944); L. Luet al., Chem. Commun., 1996, p. 2029; J. Prakt. Chem., Vol. 327 (3), pp.383-98 (1985); B. L. Feringa et al., J. Org. Chem., Vol. 53, p. 1125(1988); J. C. DeJong et al., Tetrahedron Lett., Vol. 30, p. 7239 (1989);J. C. DeJong, Ph.D. thesis, University of Groningen, The Netherlands,1991; F. A. Neugebauer et al., Chem. Ber., 1976, 109, 2389; U. Zehavi etal., J. Org. Chem., Vol. 26, pp. 1097-1101 (1961); J. March, AdvancedOrganic Chemistry, 4^(th) Edition, pp. 903 and 1091-1092, WileyInterscience (New York 1992); J. Crossley Maxwell, Aust. J. Chem., Vol.47, pp. 723-738 (1994); V. J. Wotring et al., Analytical Chemistry, Vol.62, No. 14, pp. 1506-1510 (1990); Tabushi et al., J. Am. Chem. Soc.,Vol. 103, pp. 6152-6157 (1981); T. Giorgi et al., “Gel-likelyomesophases formed in organic solvents by self-assembled guanineribbons,” Chemistry—A European Journal (2002), 8(9), 2143-2152; T.Suyama et al., “A method for the preparation of substituted biguanides,”Nippon Kagaku Kaishi (1989), (5), 884-7; Polish Patent Publication PL148060 B1; Polish Patent Publication PL 134682 B1; C. S. Snijder et al.,Chem. Eur. J., Vol. 1, No. 9, pp. 594-597 (1995); S. Senda et al., GifuColl. Pharm., Gifu, Japan. Yakugaku Zasshi (1969), 89 (2), 254-259; B.Gluncic et al, Acta Phorm. Jugosl. (1986), 36(4), 393-404; CanadianPatent Publication CA 941377; M. Klein, Recent Dev. Mass Spectrom.Biochem. Med., (Proc. Int. Symp.), 4^(th) (1978), Meeting Date 1977, 1,471-82; PCT Patent Publication WO/9011283; Japanese Patent PublicationJP 62181279; T. Wada et al., “A New Boranophosphorylation Reaction forthe Synthesis of Deoxyribonucleoside Boranophosphates,” TetrahedronLetters, Vol. 43, No. 23, pp. 4137-4140 (2002); R. Schirrmacher et al.,“Dimethylpyridin-4-ylamine-catalysed alcoholysis of2-amino-N,N,N-trimethyl-9H-purine-6-ylammonium chloride: An effectiveroute to O6-substituted guanine derivatives from alcohols with poornucleophilicity,” Synthesis, Vol. 4, pp. 538-542 (2002); Z. Situ,“Synthesis of Tricyclic Derivatives of Guanine Analogue Catalyzed byKF—Al₂O₃ ,” Huaxue Shiji, Vol. 24, No. 1, p. 57 (2002); Korean Patent2000003081 (Korean Patent Application KR 1998-24185); S. Bailey et al.,“Synthesis and Antiviral Activity of 9-Alkoxypurines: New9-(Hydroxyalkoxy) Derivatives of Guanine and 8-Methylguanine,” AntiviralChem. Chemother., Vol. 5, No. 1, pp. 21-33 (1994); Japanese PatentPublication JP 06157529; Japanese Patent Publication JP 3217541; M. R.Harnden et al., “Synthesis, Oral Bioavailability and In Vivo Activity ofAcetal Derivatives of the Selective Antiherpesvirus Agent9-(3-Hydroxypropoxy)Guanine (BRL44385),” Antiviral Chem. Chemother.,Vol. 5, No. 3, pp. 147-54 (1994); Spanish Patent Publication ES 2047457;B. K. Bhattacharya et al., “Synthesis of Certain N— and C-alkyl PurineAnalogs,” J. Heterocycl. Chem., Vol. 30, No. 5, pp. 1341-9 (1993);Polish Patent Publication PL 148969; PCT Patent Publication WO/9011283;U.S. Pat. No. 5,298,618; and Japanese Patent Publication JP 62181279,the disclosures of each of which are totally incorporated herein byreference.

U.S. Pat. No. 6,586,492 and PCT Patent Publication WO 99/54416 (Caigeret al.), the disclosures of each of which are totally incorporatedherein by reference, disclose an ink-jet ink including an ink jetvehicle and a colorant. The vehicle includes at least 35 percent byweight radiation curable material, based on the total vehicle weight.The vehicle may but does not necessarily include a thickener. Thevehicle is a paste or a solid at 20° C. and has a viscosity of less than25 centipoise between 40° C. and 130° C.

Japanese Patent Publication JP 6200204, the disclosure of which istotally incorporated herein by reference, discloses a normally solid jetrecording ink which can melt at a relatively low temperature and cancure immediately when irradiated with ultraviolet rays. The inkcomprises a wax having a melting point of 40 to 70° C., a resin having amelting point of 40 to 70° C., a prepolymer, a monomer, aphotopolymerization initiator, a dye, and a pigment. This ink isnormally solid because it contains the above-specified wax. When theultraviolet curable resin is irradiated with ultraviolet rays from anultraviolet lamp, the ink can fix immediately and satisfactorily onplain paper or printing paper.

The trans-1,2-cyclohexane bis-urea organogelator compounds exhibit somedisadvantages for performing in a phase-change solid ink vehicle, suchas high melting point and high degree of crystallinity. In addition,these compounds are commonly prepared by the reaction oftrans-1,2-diaminocyclohexane with two molar equivalents of amonofunctional isocyanate, and their large-scale commercial preparationis often limited to the use of available monofunctional isocyanate rawmaterials that are regulated for health and safety reasons.

Many currently used phase change inks require high jetting temperaturesof about 140° C. or greater and also require relatively long warm-uptimes for the printer. In addition, many currently used phase changeinks generate images with relatively poor scratch resistance andrelatively poor image permanence.

While known compositions and processes are suitable for their intendedpurposes, a need remains for improved phase change ink compositions. Inaddition, a need remains for phase change inks that can be jetted atreduced temperatures of about 110° C. or lower, thereby enabling costand energy savings. Further, a need remains for phase change inks thatenable printing with reduced printer warm-up times. Additionally, a needremains for phase change inks that generate images with improved scratchresistance. There is also a need for phase change inks that generateimages with improved image permanence. In addition, there is a need forphase change inks that generate images with improved image quality.Further, there is a need for phase change inks that exhibit theaforementioned advantages when used in a printing process wherein theink is first jetted onto an intermediate transfer member andsubsequently transferred from the intermediate transfer member to afinal print substrate such as plain or coated paper or a transparency.Additionally, there is a need for phase change inks that exhibit theaforementioned advantages when used in a printing process wherein theink is jetted directly onto a final print substrate such as plain orcoated paper or a transparency. A need also remains for phase changeinks that exhibit the aforementioned advantages when used in printingprocesses at relatively high speeds. In addition, a need remains forphase change inks having desirably low melting points that also containgelator compounds which enable additional advantages in the phase changeinks. Further, a need remains for gelator compounds for use in phasechange inks and other applications that have a desirably low degree ofcrystallinity. Additionally, a need remains for gelator compounds thatare soluble in phase change ink carriers. There is also a need for phasechange inks that exhibit an intermediate gel phase between the solidphase and the liquid phase. In addition, there is a need for phasechange inks exhibiting an intermediate gel phase wherein the gel phasetransition is desirably narrow. Further, there is a need for gelatorcompounds that enable desirably narrow gel phase transitions.Additionally, there is a need for phase change inks exhibiting anintermediate gel phase wherein the gel phase transition entails atan-delta of less than about 10. A need also remains for gelatorcompounds that enable gel phase transitions entailing a tan-delta ofless than about 10. In addition, a need remains for gelator compoundsthat are less highly crystalline and do not pack as tightly within amolecular network as do more crystalline materials, thereby enablingthem to be soluble within molten phase change inks. Additionally, a needremains for curable compounds that are soluble in phase change inkcarriers. There is also a need for curable compounds that can beincorporated into phase change ink carriers without adversely affectingthe viscosity characteristics of the ink at desired jettingtemperatures. In addition, there is a need for curable compounds thatcan be incorporated into phase change ink carriers without adverselyaffecting the melting point of the ink. Further, there is a need forcurable phase change inks that can be used in ink jet printing processeswherein the ink is first jetted onto an intermediate transfer member andsubsequently transferred from the transfer member to a final substratesuch as paper or transparency material. Additionally, there is a needfor curable phase change inks that can be used in ink jet printingprocesses wherein the ink is first jetted onto an intermediate transfermember and subsequently transferred from the transfer member to a finalsubstrate such as paper or transparency material, wherein theintermediate transfer member is maintained at a temperature between thejetting temperature of the ink and the temperature of the finalsubstrate. A need also remains for curable compounds that can beincorporated into phase change ink carriers to be used in printingprocesses using heated intermediate transfer members without adverselyaffecting the temperature at which the intermediate transfer member caneffectively transfuse the image thereon to the final substrate. Inaddition, a need remains for radiation curable compounds that undergophase change transitions within a radiation-curable ink carrier.Further, a need remains for compounds that can impart phase changecharacteristics to a radiation curable ink and that are also themselvesradiation curable. Additionally, a need remains for curable phase changeinks that can be used in ink jet printing processes wherein the ink isjetted directly onto a final substrate such as uncoated paper andwherein the ink exhibits reduced feathering on the final substrate.There is also a need for curable phase change inks that can be used inink jet printing processes wherein the ink is jetted directly onto afinal substrate such as coated paper and wherein the image exhibitsreduced pixel agglomeration on the final substrate.

SUMMARY

Disclosed herein are curable trans-1,2-cyclohexane bis(urea-urethane)compounds of the formulae

wherein R₁ and R′₁ each, independently of the other, is an alkylenegroup, an arylene group, an arylalkylene group, or an alkylarylenegroup, R₂ and R′₂ each, independently of the other, is an alkyl group,an aryl group, an arylalkyl group, or an alkylaryl group, R₃ and R′₃each, independently of the other, is a hydrogen atom or an alkyl group,R₄ and R′₄ each, independently of the other, is a hydrogen atom, afluorine atom, an alkyl group, or a phenyl group, n is an integer of 0,1, 2, 3, or 4, and R₅ is an alkyl group, an aryl group, an arylalkylgroup, an alkylaryl group, or a substituent other than an alkyl, aryl,arylalkyl, or alkylaryl group, provided that at least one of R₁, R′₁,R₂, R′₂, R₃, R′₃, R₄, R′₄, or one or more of R₅ is an alkyl, alkylene,arylalkyl, arylalkylene, alkylaryl, or alkylarylene group containing anethylenic unsaturation rendering the compound curable upon exposure toheat and/or actinic radiation.

DETAILED DESCRIPTION

The curable trans-1,2-cyclohexane bis(urea-urethane) compounds are ofthe formulae

wherein R₁ and R′₁ each, independently of the other, is (i) an alkylenegroup (including linear, branched, saturated, unsaturated, cyclic,substituted, and unsubstituted alkylene groups, and wherein heteroatoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, andthe like either may or may not be present in the alkylene group), in oneembodiment with at least about 2 carbon atoms, in another embodimentwith at least about 4 carbon atoms, and in yet another embodiment withat least about 6 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 30carbon atoms, and in yet another embodiment with no more than about 20carbon atoms, although the number of carbon atoms can be outside ofthese ranges, (ii) an arylene group (including substituted andunsubstituted arylene groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the arylene group), in one embodiment with atleast about 5 carbon atoms, and in another embodiment with at leastabout 6 carbon atoms, and in one embodiment with no more than about 18carbon atoms, in another embodiment with no more than about 12 carbonatoms, and in yet another embodiment with no more than about 6 carbonatoms, although the number of carbon atoms can be outside of theseranges, (iii) an arylalkylene group (including substituted andunsubstituted arylalkylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in either the aryl or the alkyl portionof the arylalkylene group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 30 carbon atoms, and in yetanother embodiment with no more than about 20 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as benzyleneor the like, including (a) arylalkylene groups wherein both the aryl andthe alkyl portions form the linkage between the two —NH— groups, such as

and the like, and (b) arylalkylene groups wherein only the alkyl portionforms the linkage between the two —NH— groups, such as

and the like, or (iv) an alkylarylene group (including substituted andunsubstituted alkylarylene groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in either the aryl or the alkyl portionof the alkylarylene group), in one embodiment with at least about 6carbon atoms, and in another embodiment with at least about 7 carbonatoms, and in one embodiment with no more than about 50 carbon atoms, inanother embodiment with no more than about 30 carbon atoms, and in yetanother embodiment with no more than about 20 carbon atoms, although thenumber of carbon atoms can be outside of these ranges, such as tolyleneor the like, including (a) alkylarylene groups wherein both the alkyland the aryl portions form the linkage between the two —NH— groups, suchas

and the like, and (b) alkylarylene groups wherein only the aryl portionforms the linkage between the two —NH— groups, such as

and the like, R₂ and R′₂ each, independently of the other, is (i) analkyl group (including linear, branched, saturated, unsaturated, cyclic,substituted, and unsubstituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least about 2 carbon atoms, in another embodimentwith at least about 4 carbon atoms, and in yet another embodiment withat least about 6 carbon atoms, and in one embodiment with no more thanabout 50 carbon atoms, in another embodiment with no more than about 30carbon atoms, and in yet another embodiment with no more than about 20carbon atoms, although the number of carbon atoms can be outside ofthese ranges, (ii) an aryl group (including substituted andunsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the aryl group), in one embodiment with at leastabout 5 carbon atoms, and in another embodiment with at least about 6carbon atoms, and in one embodiment with no more than about 18 carbonatoms, in another embodiment with no more than about 12 carbon atoms,and in yet another embodiment with no more than about 6 carbon atoms,although the number of carbon atoms can be outside of these ranges,(iii) an arylalkyl group (including substituted and unsubstitutedarylalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in either the aryl or the alkyl portion of the arylalkylgroup), in one embodiment with at least about 6 carbon atoms, and inanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 30 carbon atoms, and in yet anotherembodiment with no more than about 20 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as benzyl or thelike, or (iv) an alkylaryl group (including substituted andunsubstituted alkylaryl groups, and wherein hetero atoms, such asoxygen, nitrogen, sulfur, silicon, phosphorus, boron, and the likeeither may or may not be present in either the aryl or the alkyl portionof the alkylaryl group), in one embodiment with at least about 6 carbonatoms, and in another embodiment with at least about 7 carbon atoms, andin one embodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 30 carbon atoms, and in yet anotherembodiment with no more than about 20 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, R₃ and R′₃ each, independently of the other, is a hydrogen atom oran alkyl group (including linear, branched, substituted, andunsubstituted alkyl groups), in one embodiment with at least 1 carbonatom, and in one embodiment with no more than about 3 carbon atoms,although the number of carbon atoms can be outside of these ranges, R₄and R′₄ each, independently of the other, is a hydrogen atom, a fluorineatom, an alkyl group (including linear, branched, saturated,unsaturated, substituted, and unsubstituted alkyl groups, and whereinhetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus,boron, and the like either may or may not be present in the alkylgroup), in one embodiment with at least 1 carbon atom, and in oneembodiment with no more than about 6 carbon atoms, in another embodimentwith no more than about 3 carbon atoms, and in yet another embodimentwith no more than about 2 carbon atoms, although the number of carbonatoms can be outside of these ranges, or a phenyl group, n is an integerof 0, 1 2, 3, or 4, and each R₅, independently of the others, is (i) analkyl group (including linear, branched, saturated, unsaturated, cyclic,substituted, and unsubstituted alkyl groups, and wherein hetero atoms,such as oxygen, nitrogen, sulfur, silicon, phosphorus, boron, and thelike either may or may not be present in the alkyl group), in oneembodiment with at least 1 carbon atom, and in one embodiment with nomore than about 50 carbon atoms, in another embodiment with no more thanabout 30 carbon atoms, and in yet another embodiment with no more thanabout 20 carbon atoms, although the number of carbon atoms can beoutside of these ranges, (ii) an aryl group (including substituted andunsubstituted aryl groups, and wherein hetero atoms, such as oxygen,nitrogen, sulfur, silicon, phosphorus, boron, and the like either may ormay not be present in the aryl group), in one embodiment with at leastabout 5 carbon atoms, and in another embodiment with at least about 6carbon atoms, and in one embodiment with no more than about 18 carbonatoms, in another embodiment with no more than about 12 carbon atoms,and in yet another embodiment with no more than about 6 carbon atoms,although the number of carbon atoms can be outside of these ranges,(iii) an arylalkyl group (including substituted and unsubstitutedarylalkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in either the aryl or the alkyl portion of the arylalkylgroup), in one embodiment with at least about 6 carbon atoms, and inanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 30 carbon atoms, and in yet anotherembodiment with no more than about 20 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as benzyl or thelike, (iv) an alkylaryl group (including substituted and unsubstitutedalkylaryl groups, and wherein hetero atoms, such as oxygen, nitrogen,sulfur, silicon, phosphorus, boron, and the like either may or may notbe present in either the aryl or the alkyl portion of the alkylarylgroup), in one embodiment with at least about 6 carbon atoms, and inanother embodiment with at least about 7 carbon atoms, and in oneembodiment with no more than about 50 carbon atoms, in anotherembodiment with no more than about 30 carbon atoms, and in yet anotherembodiment with no more than about 20 carbon atoms, although the numberof carbon atoms can be outside of these ranges, such as tolyl or thelike, or (v) a substituent other than an alkyl, aryl, arylalkyl, oralkylaryl group, wherein the substituents on the substituted alkyl,alkylene, aryl, arylene, arylalkyl, arylalkylene, alkylaryl, andalkylarylene groups for R₁, R′₁, R₂, R′₂, R₃, R′₃, R₄, R′₄, and R₅ andthe substituents other than alkyl, aryl, arylalkyl, or alkylaryl groupscan be (but are not limited to) halogen atoms, including fluorine,chlorine, bromine, and iodine atoms, imine groups, ammonium groups,cyano groups, pyridinium groups, ether groups, aldehyde groups, ketonegroups, ester groups, carbonyl groups, thiocarbonyl groups, sulfidegroups, sulfoxide groups, phosphine groups, nitrile groups, mercaptogroups, nitro groups, nitroso groups, sulfone groups, acyl groups,urethane groups, urea groups, mixtures thereof, and the like, whereintwo or more substituents can be joined together to form a ring.

Since hetero atoms can be included in the R₁ and R′₁ groups, R₁ and R′₁also include alkyleneoxy, aryleneoxy, arylalkyleneoxy, alkylaryleneoxy,polyalkyleneoxy, alkoxyalkylene, alkoxyarylene, pyrrolidine, imidazole,pyrimidinone, oxazoline, thiazoline, and like groups, provided that nooxygen atom is directly bonded to one of the nitrogen atoms. Inaddition, since hetero atoms can be included in the R₁ and R′₁ groups,R₁ and R′₁ also include heterocyclic groups.

Since hetero atoms can be included in the R₂ and R′₂ groups, R₂ and R′₂also include alkoxy, aryloxy, arylalkoxy, alkylaryloxy, polyalkyleneoxy,alkoxyalkyl, alkoxyaryl, pyrrolidine, imidazole, pyrimidinone,oxazoline, thiazoline, and like groups, provided that no oxygen atom isdirectly bonded to one of the nitrogen atoms. In addition, since heteroatoms can be included in the R₂ and R′₂ groups, R₂ and R′₂ also includeheterocyclic groups.

Since hetero atoms can be included in the R₅ groups, these groups alsoinclude alkoxy, aryloxy, arylalkoxy, alkylaryloxy, polyalkyleneoxy,alkoxyalkyl, alkoxyaryl, pyrrolidine, imidazole, pyrimidinone,oxazoline, thiazoline, and like groups. In addition, since hetero atomscan be included in the R₅ groups, these groups also include heterocyclicgroups.

In one specific instance, R₁ and R′₁ have in one embodiment at leastabout 2 carbon atoms, in another embodiment at least about 4 carbonatoms, and in yet another embodiment at least about 6 carbon atoms,although the number of carbon atoms can be outside of these ranges.

In one specific instance, R₁ and R′₁ have in one embodiment no more thanabout 30 carbon atoms, in another embodiment no more than about 18carbon atoms, and in yet another embodiment no more than about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges.

In one specific instance, R₂ and R′₂ have in one embodiment at leastabout 4 carbon atoms, in another embodiment at least about 5 carbonatoms, and in yet another embodiment at least about 6 carbon atoms,although the number of carbon atoms can be outside of these ranges.

In one specific instance, R₂ and R′₂ have in one embodiment no more thanabout 30 carbon atoms, in another embodiment no more than about 18carbon atoms, and in yet another embodiment no more than about 12 carbonatoms, although the number of carbon atoms can be outside of theseranges.

At least one of R₁, R′₁, R₂, R′₂, R₃, R′₃, R₄, R′₄, and one or more ofR₅ is an alkyl, alkylene, arylalkyl, arylalkylene, alkylaryl, oralkylarylene group containing an ethylenic unsaturation rendering thecompound curable upon exposure to heat or actinic radiation. Examples ofethylenically unsaturated groups include (but are not limited to) alkenegroups, vinyl ether groups, allyl ether groups, acrylate groups,methacrylate groups, acrylamide groups, methacrylamide groups,norbornenyl groups, isoprenyl groups, vinyl benzoate groups, vinyl estergroups, and the like. Curing can be initiated by any desired oreffective mechanism, such as free radical, cationic, thermal, or thelike.

By “curable upon exposure to heat and/or actinic radiation” is meantthat the compound, upon exposure to heat and/or actinic radiation,reacts to convert ethylenically unsaturated carbon-to-carbon bonds tosaturated carbon-carbon single covalent bonds, thereby undergoingcrosslinking or chain extension. In many cases, the cured material canexhibit improved mechanical properties, such as greater mechanicalstrength, reduced solubility in solvents, and greater adhesion tosubstrates. Actinic radiation can be defined as radiation at wavelengthsof from about 4 to about 500 nanometers. In a specific embodiment, theradiation is at wavelengths of from about 260 to about 440 nanometers.Heat curing can occur by any desired or effective mechanism, such as bythe effect of heat upon an initiator molecule at any desired oreffective temperature, in one embodiment from about 30° C. to about 150°C., and in another embodiment from about 60° C. to about 130° C.,although the temperature can be outside of these ranges.

In one specific embodiment, R₁ and R′₁ are the same. In another specificembodiment, R₁ and R′₁ are the same and R₂ and R′₂ are the same. In yetanother specific embodiment, R₁ and R′₁ are the same, R₂ and R′₂ are thesame, R₃ and R′₃ are the same, and R₄ and R′₄ are the same. In stillanother specific embodiment, R₁ and R′₁ are the same, R₂ and R′₂ are thesame, R₃ and R′₃ are the same, R₄ and R′₄ are the same, and n is 0. Inanother specific embodiment, R₁ and R′₁ are the same, R₂ and R′₂ are thesame, R₃ and R′₃ are both hydrogen, R₄ and R′₄ are both hydrogen, and nis 0.

The trans-1,2-cyclohexane bis(urea-urethane) compounds can be preparedby any desired or effective method. For example, a monoalcohol of theformula R₂—OH can be reacted with a diisocyanate of the formulaOCN—R₁—NCO in approximately equimolar amounts at elevated temperatures,optionally in the presence of a catalyst, and optionally in the presenceof a solvent. Thereafter, the resulting product can be cooled to aboutroom temperature and reacted with about 2 moles of product per every 1mole of 1,2-diaminocyclohexane substituted as desired, optionally in thepresence of a solvent, at room temperature. The reaction proceeds asfollows (shown below without representing the stereochemistry; theasterisks indicate the chiral centers):

The monoalcohol and the diisocyanate are present in any desired oreffective relative amounts, in one embodiment at least about 0.4 mole ofmonoalcohol per every one mole of diisocyanate, in another embodiment atleast about 0.6 mole of monoalcohol per every one mole of diisocyanate,and in yet another embodiment at least about 0.8 mole of monoalcohol perevery one mole of diisocyanate, and in one embodiment no more than about1.4 moles of monoalcohol per every one mole of diisocyanate, in anotherembodiment no more than about 1.2 moles of monoalcohol per every onemole of diisocyanate, and in yet another embodiment no more than about 1mole of monoalcohol per every one mole of diisocyanate, although therelative amounts can be outside of these ranges.

Examples of suitable catalysts include (but are not limited to) Lewisacid catalysts such as dibutyl tin dilaurate, bismuth tris-neodecanoate,cobalt benzoate, lithium acetate, stannous octoate, triethylamine,ferric chloride, aluminum trichloride, boron trichloride, borontrifluoride, titanium tetrachloride, tin tetrachloride, and the like.The catalyst, when present, is present in any desired or effectiveamount, in one embodiment at least about 0.2 mole percent, in anotherembodiment at least about 0.5 mole percent, and in yet anotherembodiment at least about 1 mole percent, and in one embodiment no morethan about 10 mole percent, in another embodiment no more than about 7.5mole percent, and in yet another embodiment no more than about 5 molepercent, based on the amount of diisocyanate, although the amount can beoutside of these ranges.

Examples of suitable solvents for the first part of the reaction include(but are not limited to) toluene, hexane, heptane, methylene chloride,tetrahydrofuran, diethyl ether, ethyl acetate, methyl ethyl ketone, andthe like, as well as mixtures thereof. When present, the solvent ispresent in any desired amount, in one embodiment at least about 10milliliters per millimole of diisocyanate, in another embodiment atleast about 20 milliliters per millimole of diisocyanate, in anotherembodiment at least about 30 milliliters per millimole of diisocyanate,and in one embodiment no more than about 100 milliliters per millimoleof diisocyanate, in another embodiment no more than about 80 millilitersper millimole of diisocyanate, and in yet another embodiment no morethan about 50 milliliters per millimole of diisocyanate, although theamount can be outside of these ranges.

The diisocyanate and the monoalcohol are heated to any desired oreffective temperature, in one embodiment at least about 25° C., inanother embodiment at least about 40° C., and in yet another embodimentat least about 50° C., and in one embodiment no more than about 125° C.,in another embodiment no more than about 100° C., and in yet anotherembodiment no more than about 75° C., although the amounts can beoutside of these ranges.

The diisocyanate and the monoalcohol are heated for any desired oreffective period of time, in one embodiment at least about 5 minutes, inanother embodiment at least about 10 minutes, and in yet anotherembodiment at least about 15 minutes, and in one embodiment no more thanabout 80 minutes, in another embodiment no more than about 40 minutes,and in yet another embodiment no more than about 30 minutes, althoughthe time can be outside of these ranges.

Subsequent to the reaction between the diisocyanate and the monoalcohol,the first reaction product need not be recovered; the reaction mixturecan be cooled to room temperature and the appropriately substituted1,2-diaminocyclohexane can be added to the reaction mixture, along withadditional solvent if desired, to complete the reaction.

The first reaction product and the 1,2-diaminocyclohexane are present inany desired or effective relative amounts, in one embodiment at leastabout 1.75 moles of first reaction product per every one mole of1,2-diaminocyclohexane, in another embodiment at least about 1.9 molesof first reaction product per every one mole of 1,2-diaminocyclohexane,and in yet another embodiment at least about 2 moles of first reactionproduct per every one mole of 1,2-diaminocyclohexane, and in oneembodiment no more than about 2.3 moles of first reaction product perevery one mole of 1,2-diaminocyclohexane, in another embodiment no morethan about 2.1 moles of first reaction product per every one mole of1,2-diaminocyclohexane, and in yet another embodiment no more than about2 moles of first reaction product per every one mole of1,2-diaminocyclohexane, although the relative amounts can be outside ofthese ranges.

The first reaction product and the 1,2-diaminocyclohexane are allowed toreact at any desired or effective temperature, in one embodiment atleast about 10° C., in another embodiment at least about 20° C., and inyet another embodiment at least about 30° C., and in one embodiment nomore than about 75° C., in another embodiment no more than about 50° C.,and in yet another embodiment no more than about 40° C., although thetemperature can be outside of these ranges.

The first reaction product and the 1,2-diaminocyclohexane are allowed toreact for any desired or effective period of time, in one embodiment atleast about 5 minutes, in another embodiment at least about 10 minutes,and in yet another embodiment at least about 20 minutes, and in oneembodiment no more than about 3 hours, in another embodiment no morethan about 1.5 hours, and in yet another embodiment no more than about 1hour, although the time can be outside of these ranges.

Thereafter, the product can be precipitated by addition of a smallamount of a non-solvent, such as hexane or methylene chloride, followedby good stirring. The product can then be recovered by filtration.

While not being limited to any particular theory, it is believed thatthe trans-1,2-cyclohexane bis(urea-urethane) compounds disclosed hereinform reversible hydrogen bonds, resulting in the formation of oligomersand oligomer networks held together by non-covalent hydrogen bondsinstead of covalent bonds. One example of such bond formation isillustrated as follows:

While not being limited to any particular theory, it is believed that inthe inks containing these trans-1,2-cyclohexane bis (urea-urethane)compounds, at least some and perhaps all of these hydrogen bonds can bebroken at the temperatures at which hot melt ink jet printing occurs(typically, although not necessarily, over 100° C.). When the ink isprinted onto an intermediate transfer member or a final recordingsubstrate, the ink cools as it is printed, which results in reformationof any hydrogen bonds broken by heating. The polymer-like materials thusformed behave like conventional covalently-bonded polymers to enhanceimage permanence. The image robustness can be increased by adding atrans-1,2-cyclohexane bis(urea-urethane) gelator compound to the ink.The gelator molecules can self-assemble into 3-dimensional fibrousnetworks by intermolecular hydrogen bonding and van der Waalsinteractions. The molten ink is expected to get trapped into these gelnetworks and form a semi-solid or a gel. In addition, the gelled inksexhibit visco-elastic rheological characteristics that are differentfrom those of conventional hot melt or phase change inks in that theyshow an elastic behavior in a region where the ink is supposed to be inthe liquid state. This behavior is evidenced by the crossover of G′(storage modulus) and G″ (loss modulus), with G′ being higher than G″,indicating that the material is elastic. The elasticity of the materialcan also be expressed using tan-delta, which is defined as the ratio ofG″ to G′, or G″/G′. A material which has a tan-delta of less than one iselastic, whereas a non-elastic material will not have a tan-delta ofless than one above its melting point. The trons-1,2-cyclohexanebis(urea-urethane) gelator compounds, when present in phase change inks,can enable an intermediate gel phase wherein the gel phase transitionentails a tan-delta of in one embodiment less than about 10, in anotherembodiment less than about 5, and in yet another embodiment less thanabout 1, although the tan-delta can be outside of these ranges. Thiselasticity can further enhance the robustness of images generated withthe inks containing the trans-1,2-cyclohexane bis(urea-urethane)compounds. The trans-1,2-cyclohexane bis(urea-urethane) gelatorcompounds can also enable desirably narrow gel phase transitions in theinks, in one embodiment gel phase transitions 0.1 to 40° C. wide, inanother embodiment gel phase transitions 0.1 to 20° C. wide, and in yetanother embodiment gel phase transitions 0.1 to 15° C. wide, althoughthe gel phase transitions can be outside of these ranges.

Phase change inks as disclosed herein in one specific embodiment exhibita gel phase or state from about 1° C. to about 40° C. above the inkmelting point, in another specific embodiment exhibit a gel phase orstate from about 1° C. to about 20° C. above the ink melting point, andin yet another specific embodiment exhibit a gel phase or state fromabout 2° C. to about 15° C. above the ink melting point, although thegel phase or state can be exhibited outside of these ranges.

The formation of hydrogen-bonded oligomers or polymers from specific inkcarrier materials can be determined by any desired method. For example,a dramatic onset of resinous and viscoelastic characteristics on coolingis indicative of the formation of hydrogen-bonded oligomers or polymersfrom the ink carrier material or combination of materials. The formationof hydrogen bonds and hydrogen-bonded oligomers or polymers can also bedetected by IR spectroscopy. NMR spectroscopy may also help to detectthe presence of hydrogen-bonded oligomers or polymers. In situationswherein the ink carrier material is crystalline, X-ray crystallographycan be used to define the oligomeric or polymeric structure.

Further information on gels is disclosed in, for example, Gels Handbook,Vol. 1-4, Editors-in-Chief, Y. Osada and K. Kajiwara (translated by H.Ishida), 2001, Academic Press, the disclosure of which is totallyincorporated herein by reference.

Specific embodiments will now be described in detail. These examples areintended to be illustrative, and the claims are not limited to thematerials, conditions, or process parameters set forth in theseembodiments. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE I

To a solution containing 1,6-diisocyanatohexane (5.04 grams, 30 mmol;obtained from Sigma-Aldrich Fine Chemicals, Milwaukee, Wis.) andanhydrous tetrahydrofuran (100 milliliters) stirring at room temperaturewas added 1,4-butanediol vinyl ether (3.48 grams, 30 mmol; obtained fromSigma-Aldrich Fine Chemicals) and dibutyltin dilaurate (0.19 grams, 0.3mmol; obtained from Sigma-Aldrich Fine Chemicals) as the catalyst. Themixture was stirred and heated to an internal temperature of about 65°C. for 25 minutes. The progress of the reaction was monitored by ¹H-NMRspectroscopy for consumption of the 1,4-butanediol vinyl ether reactant,indicated by the disappearance of the —CH₂OH multiplet, which appears at3.5 ppm as a shoulder peak on the downfield end of the intermediateisocyanate product whose signal is located at 3.35-3.40 ppm. The mixturewas cooled to about 15° C. internal temperature after which to thismixture was added dropwise a solution of trans-1,2-diaminocyclohexane(1.71 grams, 15 mmol; obtained as a racemic mixture of (1R,2R and(1S,2S) stereoisomers from Sigma-Aldrich Fine Chemicals) dissolved inanhydrous tetrahydrofuran (10 milliliters). The mixture was stirred forabout 60 minutes while warming up to room temperature, and thickened toform a gelatinous slurry. FTIR spectroscospic analysis of a reactionsample showed little unreacted isocyanate (peak at 2180 cm⁻¹, sampleprepared as a KBr pellet). Any residual isocyanate was quenched byaddition of methanol (5 milliliters). The reaction mixture was thenfiltered by vacuum filtration to give a semi-solid product, which wassubsequently stirred in hexane to ensure full precipitation. The solidproduct was filtered and dried in air to give 8.17 grams of a whitepowder (79 percent yield). The product was believed to be of theformulae

¹H-NMR spectroscopic analysis of the solid was performed in DMSO-d₆ (300mHz) at high temperature (60° C.) and indicated the above structure withthe following assigned peaks: 1.05-1.90 ppm (several multiplets, 16Hintegration, 4 methylene protons from 1,4-butanediol vinyl etherportion, 8 methylene protons from the 1,6-diisocyanatohexane portion,and 4 methylene protons from the cyclohexane ring portion); 2.95 ppm(multiplet, 4H integration, —NH(C═O)NHCH₂(CH₂)₄CH₂NH(C═O)O—); 3.2 ppm(broad singlet, 1H integration, tertiary methane proton adjacent to ureagroup on cyclohexane ring); 3.70 ppm (multiplet, 2H integration,NH(C═O)O(CH₂)₄—O—C(H_(c))═C(H_(a))(H_(b))); 3.96 ppm (doublet, 1Hintegration, —O—C(H_(c))═C(H_(a))(H_(b))); 3.98 ppm (multiplet, 2Hintegration, NH(C═O)OCH₂CH₂CH₂CH₂—O—C(H_(c))═C(H_(a))(H_(b))); 4.20 ppm(doublet, 1H integration, —O—C(H_(c))═C(H_(a))(H_(b))); 5.60 ppm and5.72 ppm (broad singlets, each 1H integration, urea NH protons); 6.48ppm (doublet of doublets, 1H integration, —O—C(H_(c))═C(H_(a))(H_(b)));6.82 ppm (broad singlet, 1H integration, urethane NH proton). Elementalanalysis calculated for C: 59.80%, H: 9.15%, N: 12.31%; found for C:59.36%, H: 9.53%, N: 12.58%.

EXAMPLE II

Into a solution containing 1,12-diisocyanatododecane (5.04 grams, 20mmol; obtained from Sigma-Aldrich Fine Chemicals) and a 1:1 mixture ofhexane and tetrahydrofuran (75 milliliters) stirring at room temperaturewas added a solution containing triethylene glycol monomethacrylate(4.36 grams, 20 mmol; obtained as CD570 from Sartomer Company Inc.,Exton, Pa.) dissolved in a 1:1 mixture of hexane and tetrahydrofuran (25milliliters), and dibutyltin dilaurate (0.063 grams, 0.1 mmol; obtainedfrom Sigma-Aldrich Fine Chemicals) as the catalyst. The mixture wasstirred and heated to an internal temperature of 40° C. The progress ofthe reaction was monitored by ¹H-NMR spectroscopy for consumption of thetriethylene glycol monomethacrylate reactant. The mixture was cooled toabout 15° C. temperature, after which to this mixture was added dropwisea solution of trans-1,2-diaminocyclohexane (1.14 grams, 10 mmol;obtained as a racemic mixture of (1R,2R) and (1S,2S) stereoisomers fromSigma-Aldrich Fine Chemicals) dissolved in a 1:1 mixture of hexane andtetrahydrofuran (20 milliliters). The reaction mixture was stirred for 1hour while warming up to room temperature. FTIR spectroscospic analysisof a reaction sample showed little unreacted isocyanate (peak at 2180cm⁻¹, sample prepared as a KBr pellet). Any residual isocyanate reagentwas quenched by addition of methanol (5 milliliters). The reactionmixture was then filtered by vacuum filtration to give 10.11 grams of asolid product as a white powder (96 percent yield). The product wasbelieved to be of the formulae

¹H-NMR spectroscopic analysis of the solid was performed in DMSO-d₆ (300MHz) at room temperature (25° C.) and indicated the above structure withthe following assigned peaks: 1.10-1.80 ppm (multiplet, 24H integration,20 protons from —NH—CH₂(CH₂)₁₀CH₂—NH— portion and 4 methylene protonsfrom the cyclohexane ring portion); 1.90 ppm (singlet, 3H integration,—(C═O)C(CH₃)═CH₂); 2.95 ppm (narrow multiplet, 4H integration,—NH—CH₂(CH₂)₁₀CH₂—NH—); 3.35 ppm (multiplet, 1H, cyclohexane ringmethine proton); 3.55 ppm (narrow multiplet, 8H integration, —(CH₂—O)protons); 4.07 ppm and 4.27 ppm (broad singlets, each 2H integration,NH(C═O)OCH₂CH₂)— and —OCH₂CH₂O(C═O)—C(CH₃)═CH₂); 5.70 ppm and 5.88 ppm(broad singlet, each 1H integration, urea NH protons); 5.70 ppm and 6.18ppm (sharp singlet, each 1H integration, terminal vinyl protons—(C═O)C(CH₃)═CH₂); 7.15 ppm (broad singlet, 1H integration, urethane NHproton). Elemental analysis calculated for: C: 57.80%, H: 8.80%, N:8.99%. Found for: C: 61.39%, H: 9.28%, N: 7.96%.

EXAMPLE III

Into a solution containing 1,6-diisocyanatohexane (4.03 grams, 24 mmol;obtained from Sigma-Aldrich Fine Chemicals) and a 1:1 mixture of hexaneand tetrahydrofuran (100 milliliters) stirring at room temperature wasadded a solution containing triethylene glycol monomethacrylate (5.24grams, 24 mmol; obtained as CD570 from Sartomer Company Inc., Exton,Pa.) dissolved in a 1:1 mixture of hexone and tetrahydrofuran (10milliliters) and dibutyltin dilaurate (0.075 grams, 0.12 mmol (obtainedfrom Sigma-Aldrich Fine Chemicals) as the catalyst. The mixture wasstirred and heated to an internal temperature of 40° C. The progress ofthe reaction was monitored by ¹H-NMR spectroscopy for consumption of thetriethylene glycol monomethacrylate reactant. The mixture was cooled toabout 15° C. temperature, after which to this mixture was added dropwisea solution of trans-1,2-diaminocyclohexane (1.37 grams, 12 mmol;obtained as a racemic mixture of (1R,2R) and (1S,2S) stereoisomers fromSigma-Aldrich Fine Chemicals) dissolved in a 1:1 mixture of hexane andtetrahydrofuran (10 milliliters). The reaction mixture was stirred for 1hour while warming up to room temperature. FTIR spectroscospic analysisof a reaction sample showed little unreacted isocyanate (peak at 2180cm⁻¹, sample prepared as a KBr pellet). Any residual isocyanate reagentwas quenched by addition of methanol (5 milliliters). The reactionmixture was then filtered by vacuum filtration to give 6.13 grams of asolid product as a white powder (58 percent yield). ¹H-NMR spectroscopicanalysis of the solid was performed in DMSO-d₆ (300 MHz) at roomtemperature (25° C.) and exhibited spectral assignments that matchedthose found for the compound in Example II. The product was believed tobe of the formulae

INK EXAMPLE 1

Mixtures comprising radiation curable materials and at least oneorganogelator compound were created to serve as ink vehicles for phasechange radiation curable inks. The ink vehicle compositions containedUV-reactive diluents along with one or more organogelator compounds. Thecurable ink vehicles were prepared by weighing out the materials listedin the table below (amounts in parts by weight) and mixing them togetherwith stirring at 80° C. for about 1 hour in amber-coated containersfollowed by cooling to room temperature. SR9003 is a reactive diluentknown as propoxylated neopentylglycol diacrylate commercially availablefrom Sartomer Company Inc. (Exton, Pa.). EB812 is Ebecryl 812 polyesteracrylate oligomer commercially available from UCB Chemical Corp.(Smyrna, Ga.). SR494 and CN2300 are both multifunctional acrylateoligomers commercially available from Sartomer Company Inc. Upon coolingand equilibrating back to room temperature, the ink vehicle compositionshad thickened to turbid gels exhibiting weak to moderate gel strength.

Component Ink Vehicle 1 Ink Vehicle 2 Ink Vehicle 3 SR9003 reactive 6.586.228 6.912 diluent (Sartomer) EB812 (UCB) 1.41 1.650 1.469 SR494(Sartomer) 0 1.670 1.434 CN2300 1.41 0 0 (Sartomer) Example II 0.600.301 0 organogelator Example III 0 0 0.304 organogelator

INK EXAMPLE 2

A radiation curable phase change ink is prepared by combining 152.1grams of propoxylated neopentyl glycol diacrylate (known as SR9003obtained from Sartomer Company Inc., Exton, Pa.), 39 grams ofamine-modified polyether acrylate (PO 94F, available from BASF,Charlotte, N.C.), 6.0 grams of2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (IRGACURE 369,available from Ciba, Tarrytown, N.Y.), 4.0 grams ofisopropylthioxanthone (DAROCUR ITX, available from Ciba), and 4.0 gramsof diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (IRGACURE 819,available from Ciba) in a beaker and stirring until complete dissolutionof the initiators is achieved. The gelator of Example III is then addedin the amount of 3.2 grams and the mixture heated to 80° C. withstirring to dissolve the gelator. Propoxylated neopentyl glycoldiacrylate (50 grams) is combined with 10 grams of Microlith Blue 4G-Kpigment (available from Ciba Specialty Chemicals, Tarrytown, N.Y.) andstirred for 10 minutes. The pigment suspension is then subjected to 40seconds of ultrasonic dispersion using a Fisher Scientific SonicDismembrator 500 equipped with a Branson 1020 ultrasonic probe employinga duty cycle of 10 seconds on, 20 seconds off and an intensity settingof 85 percent. The pigment dispersion is then heated gently to 80° C.with stirring and the previously preparedorganogelator/photoinitiator/monomer/oligomer mixture also at 80° C. isslowly added to the dispersion.

Other embodiments and modifications of the present invention may occurto those of ordinary skill in the art subsequent to a review of theinformation presented herein; these embodiments and modifications, aswell as equivalents thereof, are also included within the scope of thisinvention.

The recited order of processing elements or sequences, or the use ofnumbers, letters, or other designations therefor, is not intended tolimit a claimed process to any order except as specified in the claimitself.

1. Trans-1,2-cyclohexane bis(urea-urethane) compounds of the formulae

wherein R₁ and R′₁ each, independently of the other, is an alkylenegroup, an arylene group, an arylalkylene group, or an alkylarylenegroup, R₂ and R′₂ each, independently of the other, is an alkyl group,an aryl group, an arylalkyl group, or an alkylaryl group, R₃ and R′₃each, independently of the other, is a hydrogen atom or an alkyl group,R₄ and R′₄ each, independently of the other, is a hydrogen atom, afluorine atom, an alkyl group, or a phenyl group, n is an integer of 0,1, 3, or 4, and R₅ is an alkyl group, an aryl group, an arylalkyl group,an alkylaryl group, or a substituent other than an alkyl, aryl,arylalkyl, or alkylaryl group which is a halogen atom, an imine group,an ammonium group, a cyano group, a pyridinium group, an ether group, analdehyde group, a ketone group, an ester group, a carbonyl group, athiocarbonyl group, a sulfide group, a sulfoxide group, a phosphinegroup, a nitrile group, a mercapto group, a nitro group, a nitrosogroup, a sulfone group, an acyl group, a urethane group, a urea group,or a mixture thereof, provided that at least one of R₁, R′₁, R₂, R′₂,R₃, R′₃, R₄, R′₄ or one or more of R₅ is an alkyl, alkylene, arylalkyl,arylalkylene, alkylaryl, or alkylarylene group containing an ethylenicunsaturation rendering the compound curable upon exposure to heat and/oractinic radiation.
 2. Compounds according to claim 1 wherein at leastone of R₁ and R′₁ is an alkylene group.
 3. Compounds according to claim2 wherein at least one of R₁ and R′₁ is a linear alkylene group. 4.Compounds according to claim 2 wherein at least one of R₁ and R′₁ is abranched alkylene group.
 5. Compounds according to claim 2 wherein atleast one of R₁ and R′₁ is a cyclic alkylene group.
 6. Compoundsaccording to claim 2 wherein at least one of R₁ and R′₁ is a substitutedalkylene group.
 7. Compounds according to claim 2 wherein at least oneof R₁ and R′₁ is an unsubstituted alkylene group.
 8. Compounds accordingto claim 2 wherein at least one of R₁ and R′₁ is an alkylene grouphaving hetero atoms therein.
 9. Compounds according to claim 2 whereinat least one of R₁ and R′₁ is an alkylene group having no hetero atomstherein.
 10. Compounds according to claim 2 wherein at least one of R₁and R′₁ is an alkylene group having at least 2 carbon atoms. 11.Compounds according to claim 2 wherein at least one of R₁ and R′₁ is analkylene group having at least 6 carbon atoms.
 12. Compounds accordingto claim 2 wherein at least one of R₁ and R′₁ is an alkylene grouphaving no more than 60 carbon atoms.
 13. Compounds according to claim 2wherein at least one of R₁ and R′₁ is an alkylene group having anethylenic unsaturation therein.
 14. Compounds according to claim 1wherein at least one of R₁ and R′₁ is an arylene, arylalkylene, oralkylarylene group.
 15. Compounds according to claim 14 wherein at leastone of R₁ and R′₁ is a substituted arylene, arylalkylene, oralkylarylene group.
 16. Compounds according to claim 14 wherein at leastone of R₁ and R′₁ is an unsubstituted arylene, arylalkylene, oralkylarylene group.
 17. Compounds according to claim 14 wherein at leastone of R₁ and R′₁ is an arylene, arylalkylene, or alkylarylene grouphaving hetero atoms therein.
 18. Compounds according to claim 14 whereinat least one of R₁ and R′₁ is an arylene, arylalkylene, or alkylarylenegroup having no hetero atoms therein.
 19. Compounds according to claim14 wherein at least one of R₁ and R′₁ is an arylalkylene or alkylarylenegroup having an ethylenic unsaturation therein.
 20. Compounds accordingto claim 1 wherein R₁ and R′₁ are the same as each other.
 21. Compoundsaccording to claim 1 wherein R₁ and R′₁ are different from each other.22. Compounds according to claim 1 wherein at least one of R₂ and R′₂ isan alkyl group.
 23. Compounds according to claim 22 wherein at least oneof R₂ and R′₂ is a linear alkyl group.
 24. Compounds according to claim22 wherein at least one of R₂ and R′₂ is a branched alkyl group. 25.Compounds according to claim 22 wherein at least one of R₂ and R′₂ is acyclic alkyl group.
 26. Compounds according to claim 22 wherein at leastone of R₂ and R′₂ is a substituted alkyl group.
 27. Compounds accordingto claim 22 wherein at least one of R₂ and R′₂ is an unsubstituted alkylgroup.
 28. Compounds according to claim 22 wherein at least one of R₂and R′₂ is an alkyl group having hetero atoms therein.
 29. Compoundsaccording to claim 22 wherein at least one of R₂ and R′₂ is an alkylgroup having no hetero atoms therein.
 30. Compounds according to claim22 wherein at least one of R₂ and R′₂ is an alkyl group having at least4 carbon atoms.
 31. Compounds according to claim 22 wherein at least oneof R₂ and R′₂ is an alkyl group having at least 10 carbon atoms. 32.Compounds according to claim 22 wherein at least one of R₂ and R′₂ is analkyl group having no more than 60 carbon atoms.
 33. Compounds accordingto claim 22 wherein at least one of R₂ and R′₂ is an alkyl group havingan ethylenic unsaturation therein.
 34. Compounds according to claim 1wherein at least one of R₂ and R′₂ is an aryl, arylalkyl, or alkylarylgroup.
 35. Compounds according to claim 34 wherein at least one of R₂and R′₂ is a substituted aryl, arylalkyl, or alkylaryl group. 36.Compounds according to claim 34 wherein at least one of R₂ and R′₂ is anunsubstituted aryl, arylalkyl, or alkylaryl group.
 37. Compoundsaccording to claim 34 wherein at least one of R₂ and R′₂ is an aryl,arylalkyl, or alkylaryl group having hetero atoms therein.
 38. Compoundsaccording to claim 34 wherein at least one of R₂ and R′₂ is an aryl,arylalkyl, or alkylaryl group having no hetero atoms therein. 39.Compounds according to claim 34 wherein at least one of R₂ and R′₂ is anarylalkyl or alkylaryl group having an ethylenic unsaturation therein.40. Compounds according to claim 1 wherein R₂ and R′₂ are the same aseach other.
 41. Compounds according to claim 1 wherein R₂ and R′₂ aredifferent from each other.
 42. Compounds according to claim 1 wherein R₁and R′₁ are the same as each other and wherein R₂ and R′₂ are the sameas each other.
 43. Compounds according to claim 1 wherein R₃ and R′₃ areeach hydrogen atoms.
 44. Compounds according to claim 1 wherein at leastone of R₃ and R′₃ is an alkyl group with from 1 to 3 carbon atoms. 45.Compounds according to claim 1 wherein R₃ and R′₃ are each hydrogenatoms, wherein R₁ and R′₁ are the same as each other, and wherein R₂ andR′₂ are the same as each other.
 46. Compounds according to claim 1wherein R₄ and R′₄ are each hydrogen atoms.
 47. Compounds according toclaim 1 wherein R₄ and R′₄ are each fluorine atoms.
 48. Compoundsaccording to claim 1 wherein at least one of R₄ and R′₄ is an alkylgroup.
 49. Compounds according to claim 1 wherein R₁ and R′₁ are thesame as each other, R₂ and R′₂ are the same as each other, R₃ and R′₃are each hydrogen atoms, R₄ and R′₄ are the same as each other, and R₄and R′₄ are hydrogen atoms or fluorine atoms.
 50. Compounds according toclaim 1 wherein R₁ and R₁ are the same as each other, R₂ and R′₂ are thesame as each other, R₃ and R′₃ are each hydrogen atoms, R₄ and R′₄ arethe same as each other, R₄ and R′₄ are hydrogen atoms or fluorine atoms,and n is
 0. 51. Compounds according to claim 1 of the formulae


52. Compounds according to claim 1 of the formulae


53. Compounds according to claim 1 of the formulae